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EP0656385A1 - Polyester entierement aromatique, composition realisee avec celui-ci, et article moule fabrique avec cette derniere - Google Patents

Polyester entierement aromatique, composition realisee avec celui-ci, et article moule fabrique avec cette derniere Download PDF

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Publication number
EP0656385A1
EP0656385A1 EP94918524A EP94918524A EP0656385A1 EP 0656385 A1 EP0656385 A1 EP 0656385A1 EP 94918524 A EP94918524 A EP 94918524A EP 94918524 A EP94918524 A EP 94918524A EP 0656385 A1 EP0656385 A1 EP 0656385A1
Authority
EP
European Patent Office
Prior art keywords
temperature
aromatic polyester
parts
polyester
heat
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP94918524A
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German (de)
English (en)
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EP0656385A4 (fr
Inventor
Hiroyoshi Yoneta
Satoshi Murouchi
Hideo Watanabe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
Nippon Petrochemicals Co Ltd
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Publication date
Application filed by Nippon Petrochemicals Co Ltd filed Critical Nippon Petrochemicals Co Ltd
Priority claimed from PCT/JP1994/000965 external-priority patent/WO1994029365A1/fr
Publication of EP0656385A1 publication Critical patent/EP0656385A1/fr
Publication of EP0656385A4 publication Critical patent/EP0656385A4/fr
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R25/00—Deaf-aid sets, i.e. electro-acoustic or electro-mechanical hearing aids; Electric tinnitus maskers providing an auditory perception
    • H04R25/65—Housing parts, e.g. shells, tips or moulds, or their manufacture
    • H04R25/658—Manufacture of housing parts

Definitions

  • the present invention relates to an organic material of a novel wholly aromatic polyester which has a high elastic coefficient, fluidity and heat resistance. More particularly, the invention relates to an organic material as a polymer having a specific composition and it has a high elastic coefficient which is realize by orienting the chains of molecules in the direction of the flow of material in a fluidized condition.
  • the present invention relates to component parts of electronic heating devices and oven ware which are made from the wholly aromatic polyester and are excellent in mechanical strength, heat resistance, moldability, workability and anti-electronic oven-range characteristics.
  • electronic heating devices herein referred to includes, as described later, electronic ovens, electronic ranges and electronic oven-ranges.
  • the present invention further relates to articles which are made of a heat resistant wholly aromatic polyester and are coated with fluorocarbon resin such as polyfluoroethylene.
  • plastic materials such as polymethylterpene and polysulfone are used for making cooking ware which is used in microwave ovens or electronic oven-ranges and component parts of electronic oven-ranges.
  • the methods of heating in the electronic oven-ranges are exemplified by range heating with the irradiation of microwaves and oven heating with hot air blasting and grill heating with infrared lamps.
  • the cooking ware used in electronic oven-ranges and several component parts of electronic oven-ranges are required to have various properties such as excellent heat resistance, chemical resistance and desirable external appearance. Especially, concerning the heat resistance, very severe characteristic property is required because the parts or cooking ware are exposed not only to the high-frequency heat but also to the heat of oven heating or grill heating.
  • the temperature in an electronic oven-ranges is generally about 260°C and, in the case of oven heating, the temperature becomes partially about 300°C and, in the case of grill heating, the temperature sometimes becomes above 300°C. Accordingly, the articles used for this purpose must not be deformed and must have sufficient mechanical strength in practical uses.
  • the wholly aromatic polyester has excellent properties due to its structure. Especially, in view of the heat resistance, it is the best one among all sorts of resins.
  • the wholly aromatic polyesters which are prepared from terephthalic acid, isophthalic acid, p-hydroxy benzoic acid or its derivatives, and biphenyl-4,4-diol (4,4-diphenol) or its derivatives are widely used for electric and electronic fields such as ovens and ranges because they can be shaped by injection molding, their mechanical and electrical properties are excellent and they can meet other various requirements in the use of plastic articles such as good heat resistance, chemical resistance, oil resistance, radiation resistance, and dimensional stability (e.g. Patent Publication No. Hei 4-20327).
  • the above-mentioned wholly aromatic polyesters are acceptable in the heat resistance as represented by heat distortion temperature. It is, however, pointed out as a defect that, when injection molded articles are put in an atmosphere of 300°C or above, oven-blistering (blistering caused by heat) is liable to occur in the surfaces of molded articles. When oven-blistering occurs in the surface of molded articles, the external appearance of them are spoiled resulting in the loss of their commercial value. The cause of this blistering is not always clear. Even in the case of highly heat resistant wholly aromatic polyester resin having a heat distortion temperature of above 350°C, the blistering often occurs at temperatures below 300°C.
  • oven-range parts or oven ware of molded articles are previously subjected to heat treatment at a temperature below the blistering temperature.
  • this method is not practical because the production cost is increased with lowering the yield rate.
  • the dispersion or enamel of polyfluoroethylene is applied to the surfaces of articles by spraying, brush coating or else and the coated articles are heated to a temperature above the melting point of the polyfluoroethylene, which is flowed by baking.
  • the wholly aromatic polyesters are good in the heat resistance which is represented by the heat distortion temperature thereof.
  • the wholly aromatic polyester articles are coated with polyfluoroethylene as described above, there are problems that blistering is often caused to occur in the process of heating the molded articles to temperatures of 300°C to 340°C or above and the frequency of blistering is increased resulting in the lowering of yield rate of products.
  • the heat treatment of molded articles is done prior to the coating process.
  • the heat treatment is carried out at a temperature below the melting point, for example, at a temperature which is lower than the melting point by 80°C.
  • a coating of polytetrafluoroethylene is formed on the surface of a plate.
  • the introduction of such heat treatment process causes the serious rise of production cost and the lowering of productivity in the production site, which are not desirable.
  • the wholly aromatic polyester is excellent in heat resistance, the difficulty in moldability has hitherto been pointed out. Furthermore, although the heat distortion temperature thereof is high, it has been pointed out that the oven blistering is liable to occur in the molded articles e.g. injection molded articles.
  • the melting point is made low by lowering the linearity or rigidity of polymer by means of the copolymerization of non-linear monomers such as isophthalic acid and 6-hydroxy-2-naphthoic acid; the copolymerization of monomers having soft chains such as ethylene glycol; and the copolymerization of monomers having bulky substituent groups such as chlorohydroquinone and phenylhydroquinone.
  • non-linear monomers such as isophthalic acid and 6-hydroxy-2-naphthoic acid
  • monomers having soft chains such as ethylene glycol
  • bulky substituent groups such as chlorohydroquinone and phenylhydroquinone.
  • the object of the present invention is to provide machine parts of electronic heating devices and oven ware which are excellent in mechanical strength, heat resistance, moldability and electronic oven-range resistance.
  • Another object of the present invention is to provide a fluororesin coating material using wholly aromatic polyester which can be used for applying polyfluoroethylene coating to the surfaces of molded articles without the necessity of pretreatment such as heat treatment.
  • the present inventors have carried out extensive study by synthesizing several kinds of polyesters having optical melt anisotropy in order to improve the moldability and heat resistance of structural material. As a result, the present invention has been accomplished.
  • the first point in the present invention relates to an aromatic polyester having optical melt anisotropy, which is characterized in that the polyester comprises the structural units represented by the following formulae (1) to (6): (wherein each of k, l, m, n, o, and p indicates the content (mole %) of each constituent unit in the polyester, and they have relationship of 20 ⁇ k ⁇ 80, l+m substantially equals to n+o+p, 0 ⁇ o ⁇ 10, 1 ⁇ p ⁇ 7, and 0 ⁇ m ⁇ (1+m)/2.)
  • the second point of the present invention relates to a polyester resin composition which is made by adding 95 wt.% (vs. composition) or less of an inorganic filler to the above aromatic polyester having optical melt anisotropy.
  • the third point of the present invention relates to an aromatic polyester which comprises the structural units as defined in the above first point of the present invention and which meets the following equation: Tv-Tm ⁇ +10°C (wherein Tm is a melting point (°C) which is determined by a differential scanning calorimeter (DSC) and Tv is a temperature at which the change in apparent viscosity is abruptly reduced in the change of temperature and which is measured using a capillary rheometer (stabilization starting temperature of apparent viscosity, °C).
  • Tm is a melting point (°C) which is determined by a differential scanning calorimeter (DSC)
  • Tv is a temperature at which the change in apparent viscosity is abruptly reduced in the change of temperature and which is measured using a capillary rheometer (stabilization starting temperature of apparent viscosity, °C).
  • the fourth point of the present invention relates to inner parts for electronic heaters and oven ware which are made of the aromatic polyester having optical melt anisotropy of the foregoing first point of the invention.
  • the fifth point of the present invention relates to molded articles which are made of the aromatic polyester having optical melt anisotropy of the foregoing first point of the present invention and which is applied with the coating of fluorocarbon resin.
  • the constituent unit represented by the formula (1) is derived from p-hydroxybenzoic acid (HBA)
  • the constituent unit represented by the formula (2) is derived from 4,4'-biphenol (BP)
  • the constituent unit represented by the formula (3) is derived from hydroquinone (HQ)
  • the constituent unit represented by the formula (4) is derived from terephthalic acid (TPA)
  • the constituent unit represented by the formula (5) is derived from isophthalic acid (IPA)
  • the constituent unit represented by the formula (6) is derived from 4,4'-biphenyldicarboxylic acid (BP-DC).
  • the constituent unit of equation (1) is an inevitable component.
  • the content k exceeds 80 mole %, it is not desirable because the crystalline melting point of the obtained polyester is higher than its thermal decomposition temperature and the molding is impossible.
  • the value k is lower than 20 mole %, it is not desirable because the crystal formation of polyester chains is difficult and the elastic modulus of molded articles is low and the heat resistance thereof is not high enough.
  • the constituent unit of equation (6) is also inevitable in the present invention. By applying this, the effect to improve the fluidity of polyester can be produced. Nevertheless, this effect can be produced by copolymerizing a small quantity of the material.
  • the content p of the constituent unit of equation (6) is more than 7 mole %, the preparation of polyester by the ordinary melt polycondensation method is difficult and a longer polymerization time is necessary in order to obtain a polymer of sufficient polymerization degree, as compared with the case in which the constituent unit of formula (6) is not added. For this reason, the coloring of obtained polymer is conspicuous which is not desirable in the industrial production. In addition, it is not desirable that the economical advantage in the polymer production is lost with the increase of polymerization time. If the content is less than 1 mole %, it is not desirable because the above-described effect of copolymerization in the constituent unit of equation (6) to improve the fluidity of polyester cannot be produced.
  • the more preferable content of p is 1 ⁇ p ⁇ 4.
  • the constituent unit of equation (5) is desirable for improving the moldability of obtained polyester. If the content of o exceeds 10 mole %, it is not desirable because the heat distortion temperature is lowered markedly.
  • constituent unit of equation (3) is desirable to improve the heat resistance.
  • the content m is smaller than 1. If it is larger than 1, it is not desirable because the moldability is lowered.
  • the value is more preferably 0.5 ⁇ m ⁇ (1+m)/2.
  • the value of l+m substantially equals to n+o+p.
  • the sum of the contents (mole %) of the constituent unit of equation (2) and that of equation (3) is substantially the same as the sum (mole %) of the constituent units of equations (4), (5) and (6).
  • the aromatic polyester of the present invention meets the following equation. Tv-Tm ⁇ +10°C
  • Tm is a melting point (°C) which is measured with a differential scanning calorimeter (DSC)
  • Tv is a temperature at which the change in apparent viscosity is abruptly reduced in the rise of temperature.
  • the value is the stabilization starting temperature (°C) of apparent viscosity that is measured using a capillary rheometer.
  • the aromatic polyester in which the difference of Tv and Tm, (Tv-Tm), is smaller than +10°C has a high value in heat resistance and especially, the blistering resistance is high. This value may sometimes be minus. However, it is desirable that this value is not lower than -80°C and preferably not lower than -50°C. Meanwhile, if the difference of Tv and Tm, (Tv-Tm), is larger than +10°C, it is not desirable because the heat resistance and the blistering resistance of the aromatic polyester are low. The method of practical measurement of Tv and Tm will be described later.
  • the aromatic polyester of the present invention can be produced in accordance with the conventional polycondensation method of polyester and it is not limited.
  • the following methods (1) to (4) are exemplified as typical ones.
  • HBA p-hydroxybenzoic acid
  • BP 4,4'-biphenol
  • TPA terephthalic acid
  • BP-DC 4,4'-biphenyldicarboxylic acid
  • HQ hydroquinone
  • acetylation is carried out under the refluxing of acetic anhydride.
  • deacetic acid polycondensation is carried out by raising the temperature to a range of 250 to 350°C while distilling off acetic acid, thereby obtaining polyester.
  • the time length of polymerization can be selected from the range of 1 hour to several tens hours.
  • Typical catalysts used in the polycondensation are exemplified by stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, and metallic catalysts. They are effective especially in the dephenol polycondensation.
  • melt polymerization it is possible to employ the melt polymerization together with solid phase polymerization.
  • the degree of polymerization of the polymer obtained by polycondensation through the melt polymerization can be raised by the solid phase polymerization.
  • any know method can be employed as the above solid phase polymerization.
  • it can be done by a method such that a polyester which is obtained by melt polymerization is heated in a temperature range of 250 to 350°C for 1 to 10 hours in an atmosphere of nitrogen.
  • the polymerization vessel is not especially limited. Desirable ones are stirring apparatus generally used for high viscosity reaction such as stirring vessel-type polymerization devices equipped with stirrers, for example, anchor-type stirrer, multi-stage stirrer, helical ribbon stirrer, helical screw stirrer and thier modifications. Furthermore, Warner mixer, Banbury mixer, pony mixer, Muller mixer and roll mill, and continuous type apparatus of Ko-kneader, pug mill, and gear compounder.
  • the polyester of the present invention can be copolymerized with aromatic dicarboxylic acids such as 2,6-dicarboxynaphthalene, 2,5-dicarboxynaphthalene, 3,4'-biphenyldicarboxylic acid, and 3,3'-biphenyldicarboxylic acid; aromatic diols such as resorcinol, catechol, 2,6-dihydroxynaphthalene, and 2,5-dihydroxynaphthalene; and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid; p-aminophenol and p-aminobenzoic acid as well as the monomers containing the foregoing constituent units.
  • aromatic dicarboxylic acids such as 2,6-dicarboxynaphthalene, 2,5-dicarboxynaphthalene, 3,4'-biphenyldicarboxylic acid, and 3,3'-biphenyldica
  • the melting point of polyester is obtained by measuring the peak of heat absorption in DSC (differential scanning calorimeter). More particularly, the thermal history of polyester resin to be measured is removed by any appropriate measure. After that, the temperature of the polyester resin is raised by DSC and during the rise of temperature, the heat absorption is measured. The temperature corresponding to the peak of heat absorption is regarded as the melting point of the tested resin.
  • the melting point obtained by this method is employed as a criterion for determining the molding temperature of a resin. For example, if this melting point is high, it is guessed that a high molding temperature is necessary. When molding is carried out at a temperature below this molding temperature, several troubles are caused to occur, for example, molding operation is unstable and sizes of molded articles are not accurate. In a worst case, the molding operation is impossible.
  • the molding temperature is generally close to the thermal decomposition temperature of the polyester (because the thermal decomposition temperature depends upon the interatomic bond energy, the value of the thermal decomposition temperature is not liable to vary with the kinds of polyesters). Accordingly, in order to avoid the thermal decomposition in an extreme case, the material having a low molding temperature has been demanded.
  • the "stabilization starting temperature of apparent viscosity" can be adopted as a measure for determining molding temperature. In other words, if this temperature of a polyester is low, it is possible to perform molding at a low temperature.
  • the melting point obtained by DSC measurement is high, heat distortion temperature and anti-blistering temperature (the temperature at which blistering occurs) are high. Nevertheless, the polyester of the present invention is characterized in that its molding temperature is lower than the molding temperature of conventionally known polyesters.
  • the aromatic polyester of the present invention can be prepared by appropriately combining the foregoing composition of the foregoing components and known polymerization conditions, so that the polymerization may be carried to obtain a product having the above-mentioned physical properties.
  • polyester of the present invention prepared as the above, can be incorporated with several fillers such as fibrous, granular or flaky organic and inorganic materials in order to improve mainly its mechanical strength.
  • the fibrous fillers are exemplified by inorganic fibrous materials such as glass fiber, asbestos fiber, silica fiber, silica-alumina fiber and potassium titanate fiber, and metallic fibers such as aluminum fiber, titanium fiber and copper fiber.
  • inorganic fibrous materials such as glass fiber, asbestos fiber, silica fiber, silica-alumina fiber and potassium titanate fiber, and metallic fibers such as aluminum fiber, titanium fiber and copper fiber.
  • metallic fibers such as aluminum fiber, titanium fiber and copper fiber.
  • a typical one is the glass fiber.
  • the granular fillers are exemplified by carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, silicates such as calcium silicate, aluminum silicate, talc, clay, diatomaceous earth and wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony trioxide and alumina, and several kinds of metal powders.
  • the flaky fillers are exemplified by mica, glass flakes and several kinds of metal foils.
  • the organic fillers are exemplified by heat resistant high-strength synthetic fibers such as aromatic polyester, aromatic polyamide and polyimide fibers. If necessary in the use of these fibers, it is desirable to use together a converging agent or a surface treating agent.
  • Especially desirable inorganic fillers are exemplified by talc, glass fiber, glass beads, and silica-alumina fiber.
  • the desirable talc is the one which is about 6% in weight loss by heating at 950°C and contains less than 1% of iron oxide (Fe2O3).
  • the glass fiber is commonly used as a reinforcing agent for resins. They are exemplified by short fibers called as milled glass fiber of 5-15 pm in diameter and 50-250 ⁇ m in length and long fibers called as chopped glass fiber of 2-5 mm in length.
  • Silica-alumina fibers of various compositions are commercially available as alumina fiber or silica fiber mainly containing silica and alumina. They are commonly called as ceramic fibers.
  • a typical silica-alumina fiber is prepared by electrically fusing about the same quantities of highly pure silica and alumina and blowing its fine streams of into the form of fibers with high pressure air.
  • the average fiber length is generally 20-200 ⁇ m.
  • the glass beads may be used without any treatment. However, in order to improve the affinity to resins, they can be surface-treated with aminosilane or epoxysilane coupling agent.
  • the use quantity of an inorganic filler relative to the whole composition is 95% by weight or less, preferably less than 80% by weight. If more than 95 wt.% of an inorganic filler is added, it is not desirable because mechanical strength is lowered.
  • thermoplastic resins can be added to the polyester of the present invention as far as they do not impair the object of the present invention .
  • the wholly aromatic polyester of the present invention can be used for producing several goods such as fibrous materials, films, three-dimensional molded articles, containers and hoses through known melt molding methods such as extrusion molding, injection molding, compression molding, and blow molding.
  • the molded articles of this kind are exemplified in the following passage: Electrical machine parts: hair drier parts (housing, etc.), cloth washer parts (bearing, valve, stop cock, rotor, etc.), video recorder parts (brake ring, etc.), dishwashing machine parts, coffee server parts (housing, etc.), tape recorder parts (bearing, etc.), cloth drier parts (pin, etc.), magnetic induction range parts (sensor casing, etc.), electric motor parts (commutator, brush holder, coreless motor parts, etc.), lamp holder (projector socket, halogen lamp socket, etc.), potentiometer (coil former, etc.), soldering iron parts, casserole stand, record-player parts (tone arm bearing, etc.); electronic machine parts: relay parts (housing, arc insulator, etc.), print-circuit board, switch (housing, etc.), connector, bobbin, electronic clock parts (housing, stator for trimmer capacitor, insulating material, etc
  • compressor parts piston parts (piston ring, brake, etc.), sliding parts for soy sauce manufacturing apparatus, parts of drier for paper making, spinning machine parts (spindle, pulley, clinper guide, etc.), motion picture projector parts, vending machine parts (bearing, etc.), jig for glass producing machine, jig for cathode-ray tube manufacturing machine, jig for electric wire manufacturing machine, jig for can manufacturing machine, jig for bottle manufacturing machine (feeding pawl, etc.), stern tube bearing, oilless bearing parts (oilless bearing, three-layer bearing, etc.), submerged bearing, heat resistant bearing for sterile works, roller bearing (ball-race, etc.
  • packing for packing, conveyor belt, mechanical seal, pulley, air pump (rotor, etc.), linear compressor (piston, etc.), locking device parts, reflowing solder parts, guide pin for welding, change-over valve for liquid chromatography, parts for petroleum winning pump, insulating material for pipe flange, parts for room heating pipe (insulating washer, etc.), extruder parts (dies, etc.), camera body, gas calorimeter parts (housing, etc.), sewing machine parts (cam, etc.), cigarette lighter parts (housing, etc.), dial gauge parts, insulating material for stator of refrigerator, parts for air conditioning apparatus (muffler, etc.), robot parts, bearing for oven, gasoline filter, parts for synchrotron, TLD parts (cap, etc.), abradable seal, binder for sharpening stone, simple metal mold, heat resistant fiber-reinforced table ware for airplane foods, and ski.
  • the molded articles which are made according to the present invention can be used as tray-type or box-type oven ware such as cooking wear for use in an oven or a range, particularly the cooking ware used in an electronic oven which is heated by microwave irradiation, more preferably in an electronic oven-range which is heated by microwave and oven heater system.
  • the molded articles are used for making machine parts of electronic ovens or electronic oven-ranges, which parts are exemplified by three-legged stay, bracket, turn table, rotating hub, protecting cover of top plate, and plug cover which are exposed to high temperature atmosphere. Because the electronic oven-range are exposed not only to the heat of high frequency but also to the heat of oven heater, very high thermal characteristics are required.
  • the molded articles according to the present invention can have satisfactory characteristics in the uses like this.
  • the fluorocarbon resin layer applied to the above-mentioned molded articles of the wholly aromatic polyester can be formed by coating of fluorocarbon resin or superposing a fluorocarbon resin film.
  • the fluorocarbon resin used for this coating or superposing is not limited so far as the resin is heat resistant.
  • Preferable fluorocarbon resin is polyfluoroethylene which is represented by the following general formula: (wherein each of X1 to X3 is an atom selected from fluorine, hydrogen and chlorine.)
  • the polyfluoroethylene represented by the above formula are exemplified by polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer-perfluoroalkylvinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene, chlorotrifluoroethyleneethylene copolymer, polyvinylidene fluoride, and polyvinyl fluoride.
  • polytetrafluoroethylene is desirable because the heat resistance as a coating is good.
  • an enamel which is prepared by dispersing by concentrating an emulsion of the polymer of fluorocarbon resin together with a surface active agent, or a composition of fluorocarbon resin and a heat resistant film forming resin can be used as a material for coating.
  • the heat resistant film forming resins are exemplified by polyamide imide, polyimide, precursors of them, polysulfone, polyphenylene sulfide, polyether imide and silicone resin.
  • Particular polyfluoroethylene coating agent used for baking finish layer are exemplified by enamel type materials of Polyflon TPFE Enamel (made by Daikin Kogyo Co., Ltd.) and Teflon PTFE Enamel (made by Mitsui Du Pont Fluorochemical Co., Ltd.)
  • a primer as an undercoating can be used. It is also possible to roughen previously the surface by sand blasting.
  • any of commonly employed methods can be used.
  • enamel or dispersion of polyfluoroethylene is applied to the surface of the resin by spraying or brushing, and it is then baked by heated treatment at a temperature above the melting point of the polyfluoroethylene to form a coating.
  • the molded article of the present invention is characterized in that good surface finish can be obtained even when the polytetrafluoroethylene having a high melting point is used.
  • the molded article prepared from the wholly aromatic polyester of the present invention has optical anisotropy and good fluidity which are derived from its molecular arrangement, and its mechanical properties and heat resistance are excellent.
  • the strength of the thus prepared molded article can be improved by heat treatment and, in many cases, its elastic modulus can also be improved.
  • This heat treatment is done by heating at a temperature below the melting point of the polymer under inert atmosphere (e.g. in nitrogen, argon, helium or steam), oxygen-containing atmosphere (e.g. in the air) or under a reduced pressure.
  • Fig. 1 is a graph showing the relationship between stabilization starting temperatures of apparent viscosities (molding temperatures) and heat distortion temperatures.
  • Fig. 2 is a graph showing the relationship between stabilization starting temperatures of apparent viscosities (molding temperatures) and anti-blistering temperatures.
  • the physical properties shown in examples of the present invention were determined through the following methods.
  • the temperatures determined by the following method were used as molding temperatures.
  • Melting Point DSC Apparatus (SSC-5020, made by Seiko Denshi Kogyo Co., Ltd.)
  • SSC-5020 made by Seiko Denshi Kogyo Co., Ltd.
  • Tm melting point
  • the sample is heated at a constant rate of 4°C/min from the temperature lower by 50°C than the melting point (Tm) which is previously measured by the above method, thereby measuring the temperature dependency of apparent viscosity (gradient relative to temperature) and obtaining the temperature at which the temperature dependency of apparent viscosity is abruptly lowered.
  • Tm melting point
  • the curve of viscosity change is relatively close to a straight line in the regions sufficiently higher or sufficiently lower than the point at which the change in apparent viscosity becomes abruptly small. Therefore, tangent lines are drawn at the points before and behind the temperature at which the temperature dependency of apparent viscosity is abruptly lowered.
  • test piece for heat distortion temperature was divided into two equal parts in a longitudinal direction. The thus obtained test pieces were tested according to ASTM D 256.
  • Electric Oven-Range Resistance An empty vessel or three-legged stay was placed on the turn table of an electronic oven-range (RE-HL10, made by Sharp Corporation). After it was heated by the range heater for 10 minutes, oven heating was carried out for 30 minutes at a preset temperature of 300°C. After that, the sample was taken out and external appearance was observed. Furthermore, another sample was subjected to range heating for 10 minutes, which was followed by grille heating for 30 minutes. After that it was taken out and the external appearance was observed.
  • polyesters prepared in the following examples had optical anisotropy when they were melted by heating.
  • a polymerization vessel having an anchor-type stirrer was used. To the polymerization vessel having a small clearance between the vessel wall and stirring blade, were fed 1,105.44 g (8.00 moles) of p-hydroxybenzoic acid (HBA), 659.93 g (3.544 moles) of 4,4'-biphenol (BP), 631.29 g (3.80 moles) of terephthalic acid (TPA), 48.45 g (0.20 mole) of 4,4'-biphenyldicarbxylic acid (BP-DC), and 52.85 g (0.48 mole) of hydroquinone as shown in Table 1.
  • HBA p-hydroxybenzoic acid
  • BP 4,4'-biphenol
  • TPA terephthalic acid
  • BP-DC 4,4'-biphenyldicarbxylic acid
  • hydroquinone as shown in Table 1.
  • deacetic acid polymerization was carried out by raising temperature to 300°C at a rate of 1°C/min, maintaining for 1 hour, further raising temperature to 330°C at the same rate, and maintaining for 20 minutes. After that, the obtained polymer was taken out from an outlet port.
  • the polymer was pulverized and was subjected to heat treatment at 280°C for 2 hours, 300°C for 2 hours and further 320°C for 5 hours in a nitrogen atmosphere.
  • the heat treated polymer and milled glass fiber in a weight ratio of 60/40 were mixed together and test pieces were made from the mixture by injection molding. The operation of injection molding was done stably.
  • HBA p-hydroxybenzoic acid
  • BP 4,4'-biphenol
  • TPA terephthalic acid
  • BP-DC 4,4'-biphenyldicarbxylic acid
  • hydroquinone hydroquinone
  • HBA p-hydroxybenzoic acid
  • BP 4,4'-biphenol
  • TPA terephthalic acid
  • IPA isophthalic acid
  • BP-DC 4, 4'-biphenyldicarbxylic acid
  • deacetic acid polymerization was carried out by raising temperature to 300°C at a rate of 1°C/min, maintaining for 1 hour, further raising temperature to 330°C at the same rate, and maintaining for 1 hour. After that, the obtained polymer was taken out from an outlet port.
  • the polymer was pulverized and was subjected to heat treatment at 250°C for 1 hour, 280°C for 2 hours, 300°C for 2 hours and further 320°C for 5 hours in a nitrogen atmosphere.
  • the heat treated polymer and milled glass fiber in a weight ratio of 60/40 were mixed together and test pieces were made from the mixture by injection molding. The operation of injection molding was done stably.
  • HBA p-hydroxybenzoic acid
  • BP 4,4'-biphenol
  • TPA terephthalic acid
  • IPA isophthalic acid
  • Ph-HQ phenylhydroquinone
  • HBA p-hydroxybenzoic acid
  • BP 4,4'-biphenol
  • TPA terephthalic acid
  • IPA isophthalic acid
  • the wholly aromatic polyesters of the monomer compositions in Example 1 to 5 in Table 1 were mixed with milled glass fiber in a weight ratio of 60/40, and the mixtures were melted and kneaded at 400°C using a twin screw extruder (PCM-30, made by Ikegai Iron Works, Ltd.) to obtain their pellets.
  • PCM-30 twin screw extruder
  • test pieces for tensile test and heat distortion temperature measurement were made by using an injection molding machine (SG-25, made by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 400°C and a metal mold temperature of 150°C.
  • the molded articles made of the wholly aromatic polyesters of the present invention were good in the balance between the mechanical strength (tensile strength, Izod impact strength) and the heat resistance (heat distortion temperature) and were excellent in anti-electronic oven-range characteristics. Especially, any blistering was not observed in the grill heating. They had excellent characteristics as the parts of electronic oven-range and as oven ware.
  • the wholly aromatic polyesters of the monomer compositions in Example 1 to 4 in Table 1 were mixed with milled glass fiber in a weight ratio of 60/40, and the mixtures were melted and kneaded at 400°C using a twin screw extruder (PCM-30, made by Ikegai Iron Works, Ltd.) to obtain their pellets.
  • PCM-30 twin screw extruder
  • 20 test pieces for bending test were made by using an injection molding machine (SG-25, made by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 400°C and a metal mold temperature of 150°C.
  • the obtained molded articles were coated with polyflon enamel (fluorocarbon resin of polytetrafluoroethylene, made by Daikin Kogyo Co., Ltd.) and baked at 340°C. The surface conditions of these test pieces were observed.
  • the wholly aromatic polyester of the present invention is excellent in moldability and is improved in the heat distortion temperature and blistering resistance.
  • the heat distortion temperature and anti-blistering temperature are high.
  • the electronic oven-range interior parts and oven ware made of the wholly aromatic polyester of the present invention has good balance between the mechanical strength and the heat resistance and excellent in anti-oven range characteristics. Therefore, they are suitable as oven ware and interior parts for electronic oven-ranges.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
EP94918524A 1993-06-15 1994-06-15 Polyester entierement aromatique, composition realisee avec celui-ci, et article moule fabrique avec cette derniere. Ceased EP0656385A4 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP16865493 1993-06-15
JP168656/93 1993-06-15
JP168654/93 1993-06-15
JP16865693 1993-06-15
JP168655/93 1993-06-15
JP16865593 1993-06-15
PCT/JP1994/000965 WO1994029365A1 (fr) 1993-06-15 1994-06-15 Polyester entierement aromatique, composition realisee avec celui-ci, et article moule fabrique avec cette derniere

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EP0656385A1 true EP0656385A1 (fr) 1995-06-07
EP0656385A4 EP0656385A4 (fr) 1997-10-22

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000019769A1 (fr) * 1998-09-25 2000-04-06 Beltone Netherlands B.V. Element d'otoplastie pour prothese auditive
WO2001004190A1 (fr) * 1999-07-12 2001-01-18 E.I. Du Pont De Nemours And Company Revetement de polymeres cristallins liquides avec des polymeres fluores
KR101757308B1 (ko) 2015-11-13 2017-07-12 세양폴리머주식회사 유동성이 향상된 전방향족 폴리에스테르 수지의 제조방법 및 이에 따라 제조된 전방향족 폴리에스테르
KR101792873B1 (ko) 2015-11-13 2017-11-20 세양폴리머주식회사 전방향족 폴리에스테르 수지의 제조방법 및 이에 따라 제조된 전방향족 폴리에스테르
US9970545B2 (en) 2015-04-17 2018-05-15 Mide Technology Corporation Stern tube seal system

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE50008B1 (en) * 1979-09-10 1986-01-22 Dart Ind Inc Improvements in or relating to plastics ovenware
JPS61199821A (ja) * 1985-03-01 1986-09-04 住友化学工業株式会社 非粘着性を有するプラスチックオ−ブンウエア
EP0394813A3 (fr) * 1989-04-26 1992-04-08 The Dow Chemical Company Copolyesters termotropes, aromatiques transformable à l'état fondu et procédé pour leur préparation

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000019769A1 (fr) * 1998-09-25 2000-04-06 Beltone Netherlands B.V. Element d'otoplastie pour prothese auditive
WO2001004190A1 (fr) * 1999-07-12 2001-01-18 E.I. Du Pont De Nemours And Company Revetement de polymeres cristallins liquides avec des polymeres fluores
US9970545B2 (en) 2015-04-17 2018-05-15 Mide Technology Corporation Stern tube seal system
KR101757308B1 (ko) 2015-11-13 2017-07-12 세양폴리머주식회사 유동성이 향상된 전방향족 폴리에스테르 수지의 제조방법 및 이에 따라 제조된 전방향족 폴리에스테르
KR101792873B1 (ko) 2015-11-13 2017-11-20 세양폴리머주식회사 전방향족 폴리에스테르 수지의 제조방법 및 이에 따라 제조된 전방향족 폴리에스테르

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